Oil composition



- densation product.

' the invention.

reamed Oct. 21,1941

nause- STA-'lES OIL COMPOSITION Herbert John West, Riverside, and Ralph Earl Layman, Jr., Old Greenwich, Conn., assignors to American Cyanmid Company, New York, N. Y.,

a corporation oi Maine No Drawing. Application February 25, 1939, Serial No. 258,566

9 Claims. (on. zoo-=21) This invention relates to' aminotriazine-resinmodified oil compositions containing glyceride oils together with aminotriazine-aldehyde condensation products. The invention includes the compositions themselves, their methods 01 manu- 5 lecture, and paints, varnishes and enamels con taining them. i s

- We have found that thefiJm-iorming characteristicsoi glycerine oils such as nonryins semi-drying anddrying oilsare greatly improved by the incorporation of aminotriazine-aldehyde condensation products therein. Drying and semidrying oilscontaining such condensation prod-' ucts will bake to films of greater hardness, water resistance and colorretention than will the un treated oils, and improved baking enamels can also be prepared irom non-drying oils such as coconut oil, castor oil and the like.

We have found that-the product obtained upon refluxing uncured aminotriazine-aldenyde condensation-products with acidified alcohols can be heatedwlth glyceride oils at temperatures as high as 180-220 0. without gelation or premature resiniflcation, and that a clear and uniform dispersion of the resin in the oil is obtained by" holding the mixture at these temperatures 101 suitable periods of 'time. The process of our invention therefore comprises, a method oi producing a solution-or miiiorm dispersion of an aminotriazine-aldehydecondensat'ion product in 3 a non-drying, semi-drying or drying lyceride oil a by heating a mixture of the oil and the reaction product of an acidified alcohol with an incom pletely polymerized aminotr'iazinealedhyde' con- I, :15 The broad principles of. our invention arenot limited to any single .aminotriazine-aldehyde condensation product, and any resinophoric material of this class may be used if desired, However, the condensation products of melamine and 0 its derivatives such as 2.4.6-triethyl and triphenyl triamino 1.3.5 triazines, 2.4.6 trihydrazino 1.3.5, triazine and the corresponding condensed triazines such as melam and melem appear at the present time to be or greatest immediate com- 45 mercial importance, by reason oi the availability of melamine and its derivatives from dicyanvdiamide or cyanuric chloride as raw materials,

and for this reason glycerlde oil compositions containing these classes 0! materials in uniform to dispersion constitute preferred embodiments of 7 On the other hand, triazines containing one or two reactive amino groups such as ammeline, ammelide, iormoguanamine, 2 amino 1.3.5 triazine and their substitution products 55 as well as nuclear substituted .aminotriazines such as 2 chloro 4.6 diamino 1.3.5 triazine, 2

phenyl 4 amino 6 hydroxy 1.3.5v triazine, 6 methyl j V 2.4 diamino 1.3.5'triazine and the like can be condensed with lower or higher aliphatic, aromatic or heterocyclic aldehydes to produce products. capable oi'improving the properties of glyceride oils, and such condensation products are therefore included in the invention in its broader aspects.

Any of the foregoing aminotriazines, includ--,

ing melamine, substituted melamines and melamine derivatives, can be condensed with any suitable aldehyde 0! the aliphatic, aromatic or heterocyclic series such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, hexaldehyde, heptaldehyde, crotonaldehyde, a11y1alde-' hyde, benzaldehyde, cinnamylaldehyde, furiural and the like to produce incompletely polymerized condensation products which can be uniformly dispersed in glycerideoilsin accordance with the principles of the invention.

The condensation between the aminotriazine and the aldehyde may take place under acid, neutral or alkaline conditions, and in the'presence or absence of a solvent for the incompletely polymerized reaction products which are first formed. rThese condensation products may be prepared by any suitable process and in any .desired combining ratio of aldehyde to amino-triazine from'lzl up to and including 6:1. -'1hcy may then be allwlated by any desired method,

such as by heating with an acidified solution of any suitable alcohol such as methanol, propanol,

butanol, cyclohexanol, amyl alcohol or the mixture of isomeric amyl alcohols known commercially as Pentaso For example a-two-stage process may be used in which the amino-triazine and aldehyde are condensed at a pH of I or higher and the resulting condensation product is dispersed in the alcohol at a pH of less than'fi, or a one-stage process in which both the initial condensation of the aminotriazine and the aldehyde and the subsequent dispersion in alcoh'ol are carried out ata pH of less than 6.

. It is known that aminotrlazlne-aldehyde condensation products can be completely polymerized by heating in the presence 0! suitable catalysts or curing agents to the stage in which they are imoluble in oils. The-saine is true with many classes of alkylated aminotriazine-aldehyde condensation products. Obviously such completely reacted condensation products are excluded from the scope of the present invention, and the term incompletely polymerized aminotriazinealdehyde condensation prod'u or similar terms having the same meaning will be used to indicatethat the condensation prodnets contemplated by the present invention are not reacted to the flnal, oil-insoluble stage.

As has been pointed out any of the products obtained by reacting anacidifled' alcohol with an incompletely polymerized amino-triazine-aldej hyde condensation product-wean be dissolved or a uniformly dispersed in glyceride oils by heating to high temperatures. Any of the oils now used in the paint and varnish industries may be mo'difled in thismanner such as linseed oil, perilla oil, soya bean oil, tung oil or oiticica oil as well as other drying oils of similar character such as flsh oils, saiilower oil, poppy seed oil, walnut oil. cedar nut oil, hempseed oil and the like.

' Representative semi-drying oils which may be modified by the-same procedure are cottonseed oil, sunflower oil, corn oil and apricot oil. The invention may also be advantageously applied to non drying oils such asjzastor oil, coconut oil. olive oil."almond oil and the like for the production of yarnishes and lacquers. oils, either singly or in admixture, may be heated with any'alcohol reacted, incompletely polymeruct to "produce glyceride oil compositions in cluded within the scope of the invention.

The incompletely polymerized alcohol reacted aminotriaaine-aldehyde condensation product ay be hiixed, with the oil either .in solidform i or as afisolution in any suitable solvent. In most it is preferable to use the alcohol reacted ,"condensatio'n product in the form of a solution as solvents are usually necessary in their prepa-' "ration; Thus. for exampleflwhen the condensajtlonprodu'ct is reacted' by heating with an exgcess'oiqan acidifled alcohol theproduct is obta'ined'as 'an alcoholic solution which may he mi'xeddirectIy" with a glyceride oiland heated to obtaina uniform dispersion. ternatively,

however; itis possible to dry the alcoholic 501" tion by vacuum drying at low temperatures and {i obtain theincompletely polymerized alcohol re-' acted condensation product in solid form, and the invention also includes the production of dispersions of such solids in g'lyc'eride oils withor "without heating. 4

I .Wi'thfmost aminotriazine-aldehyde condensatijon products, an'dparticularly with the melfamine forma1dehyde condensation products wmcn rorm the preferred modifying agents of Zjth present invention, we have found that the miixtiire of oil and condensation product is most uit ly "blended when -it is heated slowly .to j 22o; o. and maintained within this temperange for/a period of -25 minutes. when "ndensationf product is added to the' oil solvent usually distills off during the am 'hol jreacted aminotriazine-aldehyde condensation. bduct itself is .alsoevolved during. this v .period',;as' ell as a certain amount of aldehyde, fee that when the upper temperature range of L, 0:0. is reached there is formed a true solution ofthe condensation product inthe oil. "heating is'continuedat these high tempera hm uniform blendis obtained, after j as may be "allowed tocool and byQthe. following specific examples. It

Any of these isedaminotriazine-aldehyde condensation prodtion in a solvent such as an alcohol of-theheatmg period; Alcohol from noon willbe'illustrated in greater as be understood, however. that although.

these examples describe certain of the more specific features of the invention they are given primarily for illustrative p ses. and that the invention in its broader aspects is not limi thereto.

Example 1 of the above solution to 210 C. and held at this mperature for minutes. The resulting oil Example 2 183 parts by weight of 87% formaldehyde solution are adjusted with sodium hydroxide to a pHof 7.5. 63 parts of melamine are added and equipped with a stirrer and reflux condenser. After refluxing with agitation for about one hour 320 parts of n-but'anol'acidiiiedwith lpart of 85% phosphoric acid are slowly added.

The solution is refluxed for about one hour longer after which the mixture'is dehydrated by distilling off a butanol-water mixture. The distiilation is continued with addition of further stantially anhydrous.

' 100 parts of this solution were'adiusted 'to 50% solids content and mixed with 100 parts 6 of soya bean oil. The mixture was heated slowminutes, or until no more alcohol. or formaldehyde was released. The oil mixture was then eellentcharacteristics.

' Example 3 I 110mm of 2.4 'diamino 1.3.5 a; heated with 243 parts of 37% formaldehyde solution for about 4 hours, 0 until a clear solution is obtained. 400 parts of cyclohexanol containing 1 part of 85%.ph0sphoricacid are added 5 tent has been removed. Additional cyclohex- 5 the end a solution tained.

V 200parts ofsoya'bean oil are mixed with parts'of the above solution and heatedslowly to 200-220' C. and held at these temperatures until of 50% solids content is obresulting composition is well suited for the malufacture-of'varnishes having improved hardness and water resistance. a w

ma I ammeline are mixed with 488 used with similar i 127 parts 'of id solution is added until the ture is '8.0. This -mixture is refluxed for 2-3 hours, or until reaction is complete; after which 200 part of butanol are added and suliicient 75 Phosphoric acid, to neutralize after cooiing has a viscosity of 8, contains no free butanol and will bake to a hard, clear iilm.

the mixture is heated to boiling ina vessel amouhts of butanol until the solution is sub-.

1y to 200 0., collecting the' alcoholthatdistilled oil, and held between 180-200 C. for 20 cooled and constituted a bakingv varnish of ex- .and the mixture is boiled until all its water c'onanql'is added dehydration so that at a no more alcohol or formaldehyde is evolved. The

. Instead of son-bean oil. oiticica 9i! parts of, 37% formaldehyde and sodium hydrox pH of the mix-' thefreealkaliand'.

more butanol is liberated,,after which it is cooled. It constitutes an excellent vehicle for the preparation of lithographicv inks.

Example 5 200 parts of the butylated melamine-formaldehyde solution described in Example 1 are mixed with 100 parts of cottonseed oil and the mixture is heated slowly to 200 C. When evolution of butanol has'stopped, the mixture is cooled. The resulting solution'is well suited for use in admixture with alkyd resins such as oil-modified phthalic glyceride resins, or' with urea-formaldehyde resins in the preparation of paints, varnishes and enamels. For example, moles ofv formaldehyde in the form of a 37% solution may be heated with 2 moles of urea for about 2 hours, an excess of butanol added, and the heating continued until an organic solvent soluble material is obtained. 100 parts of this urea resin solution of 50% solids content may be mixed with 100 parts of the above described oil composition together with 20 parts 'of Toluidine Red Toner.

The mixture when thinnedto spraying consistency with coal tarnaphtha forms a red baking enamel that is well suited for application to sheet metal, bicycle frames, wood surfaces and the like either directly or over a primer. After application the enamel may be baked at temperatures of 225-350 F. for periods as short as 5-15 minutes and will produce a hard and glossy Example 6 200 parts of a 50% butanol solution of butylated hexamethylol melamine prepared as in Example 1 are mixed with 100-500 parts of raw or kettle-bodied linseed oil. The product may be directly. used as 'avarnish, with or without the addition of suitable amounts of driers, and is suitable for direct application to wood or sheet metal surfaces. When baked at temperatures of 150-350? F., depending on the type of surface to which it is applied, it forms a hard, clear and acting an incompletely polymerized aminotriazine-aldehyde condensationproduct with an alcohol and continuing the heating until no more alcohol is evolved.

2. A composition comprising essentially the solution obtained by heating a triglyceride oil at 180-220 C. with the product obtained upon reacting an incompletely polymerized melaminealdehyde condensation product with an alcohol and continuing the'heating until no more alcohol is evolved.

3. A composition comprisingessentially the so- I lution obtained by heating a triglyceride drying ,merized aminotriazine-aldehyde oil at -220 C. with the product obtained upon reacting an incompletely polymerized melaminealdehyde condensation product with an alcohol and continuing the heating until no more alcohol is evolved.

4. The method of obtaining a solution of an aminotriazine-aldehyde condensation product-in a triglyceride oil which comprises heating the oilat 180-220 C. with the product obtained upon reacting an incompletely polymerized aminotriazine-aldehyde condensation product with an alcohol, and continuing the heating until no more alcohol is evolved.

5. The method of obtaining a solution of a melamine-aldehyde condensation product in a triglyceride oil which comprises heating the oil at 180-220 C. with the product obtained upon reacting an incompletely polymerized melaminealdehyde condensation product with an alcohol, and continuing the heating until no more alcohol is evolved. I

6. The method-of obtaining a solution of a melamine-formaldehyde condensation product in a triglyceride oil which comprises heating the oil at 180-220" C. with the product obtained upon reacting an incompletely polymerized melamineformaldehyde condensation product with an alcohol, and continuing the heating until no more alcohol is, evolved. t

7. The method of obtaining a solution of an aminotriazine-aldehyde condensation product in a triglyceride drying oil' which comprises heating the drying oil at 180-220 C. with the product obtained upon reacting an incompletely polycondensation product with an alcohol, and continuing the heating until no more alcohol is evolved.

8. The method of obtaining a solution of a melamine-aldehyde condensation product in a triglyceride drying oil which comprises heating the drying oil at 180-220 C. with the product obtained upon reacting an incompletely polymerizedmelamine-aldehyde condensation product with an' alcohol, and continuing the heating until no more alcohol is evolved.

9. The method of obtaining a solution of a melamine-formaldehyde condensation product in a tryglyeeride drying oil which comprises heat-g ing the drying oil at 180-220 C. with the product obtained upon reacting an incompletely polymeri'zed' melamine-formaldehyde condensation product with an alcohol, and continuing the heating until no more alcohol is evolved.

. HERBERT J. WEST.

RALPH EARL LAYMAN, J5. 

